EP1079950B1 - Poudres de metal et d'alliage pour le frittage, a utiliser dans la metallurgie des poudres, leur procede de production et leur utilisation - Google Patents
Poudres de metal et d'alliage pour le frittage, a utiliser dans la metallurgie des poudres, leur procede de production et leur utilisation Download PDFInfo
- Publication number
- EP1079950B1 EP1079950B1 EP99923562A EP99923562A EP1079950B1 EP 1079950 B1 EP1079950 B1 EP 1079950B1 EP 99923562 A EP99923562 A EP 99923562A EP 99923562 A EP99923562 A EP 99923562A EP 1079950 B1 EP1079950 B1 EP 1079950B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- carboxylic acid
- precipitation
- metal salt
- aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
Definitions
- the present invention relates to a method for producing metal powders, consisting of one or more of the elements Fe, Ni, Co, Cu, Sn and possible Additions of Al, Cr, Mn, Mo and W.
- Alloy powders have a variety of applications for the production of sintered materials by powder metallurgy.
- the main feature of powder metallurgy is it that corresponding powdered alloy or metal powder is pressed and are then sintered at an elevated temperature.
- This method is in introduced on an industrial scale for the production of complicated moldings that otherwise only produce with a high degree of elaborate finishing to let.
- the sintering can be as solid phase sintering or to form a liquid phase, e.g. with hard or heavy metals.
- a very important applications of alloy and pure metal powders are tools for Metal, stone and woodworking. In these cases, they are two-phase Materials, the hardness carriers (e.g.
- the element cobalt plays a special role because it has some special properties as a metallic matrix in diamond and hard metal tools. Because it wets tungsten carbide and diamonds particularly well, it is traditionally preferred for both types of tools.
- the use of cobalt for the metallic binder phase in composite materials based on tungsten carbide or diamond achieves particularly good adhesion of the hardness carrier in the metallic binder phase. It is important to note that in the case of cobalt, the tendency to form carbides of the Co3W3C type ("eta phases"), which lead to embrittlement in hard metals, is less pronounced than, for example, in the case of iron. Co also attacks diamonds less than, for example, iron, which easily forms Fe 3 C. For these technical reasons, cobalt is traditionally used in the carbide and diamond tool industry.
- the production of hard metals is generally based on cobalt metal powders 0.8 to 2 ⁇ m FSSS (ASTM B330), which together with the Hard materials, pressing aids and a grinding fluid in air gates or ball mills, which contain carbide balls as grinding media, a mixed grinding be subjected.
- the suspension obtained is then from the grinding media separated, spray dried, and the granules obtained pressed into molds.
- the subsequent liquid phase sintering at temperatures above the melting point of the W-Co-C eutectic results in dense sintered bodies (hard metals).
- a An important property of the hard metals produced in this way is their strength Porosity is weakened.
- a porosity is called the microporosity
- B porosity is the macroporosity represents.
- cobalt metal powders are ductile and are used in the mixed grinding is not crushed, but plastically deformed or the existing ones Agglomerates disassembled. If the cobalt metal powder used sintered compactly, contain large agglomerates, they are deformed into the Spray granules transferred and result in the sintered hard metal A and B porosity, often associated with local enrichment of the binder phase.
- Diamond tools as a second important application group contain as cutting or active grinding parts sintered parts (segments), which mainly consist of Diamonds embedded in a metallic binder phase, mainly cobalt, consist.
- sintered parts which mainly consist of Diamonds embedded in a metallic binder phase, mainly cobalt, consist.
- hard materials or other metal powders may also be used to adjust the wear behavior of the bond on the diamond and the added to machined materials.
- segments Metal powder, diamonds and optionally hard material powder mixed, if necessary granulated and dense in hot presses at elevated pressure and temperature sintered.
- the requirements placed on the binder metal powder in addition to the necessary chemical purity are: good compressibility, the highest possible sintering activity, one matched to the diamond and the medium to be processed Hardness, adjusted by the grain size and the tendency to coarsen the structure during sintering, as well as slight attack on the metastable at sintering temperature Diamonds (graphitization).
- the porosity decreases with increasing sintering temperature, i.e. the density of the Sinter institutionss approaches its theoretical value. For strength reasons therefore the sintering temperature chosen as high as possible.
- the hardness falls the metallic matrix above an optimal temperature, since it is too a coarsening of the structure comes.
- at higher temperature leads to an increased attack on the diamond.
- such binder powder should be preferred for segments, if possible low sintering temperatures already reach their theoretical density and can be easily compacted.
- a disadvantage in the production of diamond tools using metal powders of the individual elements as well as of bronze powders is that the metallic Binding after sintering is very inhomogeneous, since the sintering temperature and time Homogenization is not enough. Also occur when using ferrous metal powders high pressing forces, which wear the pressing tools, and too low strength of the green compacts (e.g. edge breakouts). This too is attributed to the cubic, body-centered lattice type of iron, which has fewer sliding planes than the face-centered cubic types of cobalt and Nickel or copper metal powder. They also include the finer ones available Carbonyl iron powder high amounts of carbon, leading to loss of strength of the segment can lead. There are no atomized metal powders or alloys sufficient sintering activity so that at temperatures acceptable for diamonds sufficient compression has not yet taken place.
- the object of the invention is metal and alloy powder containing at least one of the metals iron, copper, tin, cobalt or nickel that the named Meet the requirements for binder metals for hard metals and diamond tools, to provide.
- the metal and alloy powders according to the invention can by doping with the elements Al, Cr, Mn, Mo and / or W in subordinate Amount modified and adapted to special requirements.
- the invention relates to a method for producing the metal and Alloy powder according to claim 1.
- the precipitation product is preferably included Washed water and dried.
- the precipitation product is preferably reduced in a hydrogen-containing one Atmosphere at temperatures between 400 and 600 ° C.
- the reduction can be in the indirectly heated rotary kiln or in the push-through furnace at low Cover the bed.
- Other ways to do the reduction are readily known to the person skilled in the art, e.g. in the deck oven or in the Fluidized bed.
- the calcination causes the precipitation product consisting of polycrystalline particles or agglomerates the gases released upon decomposition of the carboxylic acid residue are crushed by decrepitation is, so that for the subsequent gas phase reaction (reduction) larger surface is available and a finer end product is obtained.
- calcination in an oxygen-containing atmosphere that a metal or alloy powder is formed, which is compared to the direct reduction has a significantly reduced porosity.
- the carboxylic acids are aliphatic or aromatic, saturated or unsaturated Mono- or dicarboxylic acids, especially those with 1 to 8 carbon atoms, are suitable. Due to their reducing effect, formic acid, oxalic acid, acrylic acid and crotonic acid preferred, due to their availability in particular Formic and oxalic acid. Oxalic acid is particularly preferably used.
- the surplus reducing carboxylic acids prevents the formation of Fe (III) ions that would cause problems with the precipitation.
- the carboxylic acid is preferably in a 1.1- to 1.6-fold stoichiometric excess based on the metals used.
- a 1,2- is particularly preferred 1.5 times excess.
- the carboxylic acid solution used as a suspension that contains undissolved carboxylic acid suspended does not contain a depot dissolved carboxylic acid, from the carboxylic acid extracted by precipitation of the solution is replaced so that a high concentration during the entire precipitation reaction of carboxylic acid is maintained in the mother liquor.
- the Concentration of dissolved carboxylic acid in the mother liquor at the end of the precipitation reaction still at least 20% of the saturation concentration of the carboxylic acid in Amount of water.
- the concentration is particularly preferred of dissolved carboxylic acid in the mother liquor still 25 to 50% of the saturation concentration the carboxylic acid in water.
- a chloride solution is preferably used as the metal salt solution.
- concentration of the metal salt solution is about 1.6 to 2.5 mol per liter.
- the metal salt solution preferably has a content of 10 to 90% by weight of iron based on the total metal content and at least one other of the elements Copper, tin, nickel or cobalt.
- the content of is particularly preferably Iron in the metal salt solution at least 20 wt .-%, more preferably at least 25% by weight, very particularly preferably at least 50% by weight, but less than 80% by weight, very particularly preferably less than 60% by weight, in each case based on the total metal content.
- the metal salt solutions more preferably contain 10 to 70% by weight, in particular preferably up to 45% by weight, cobalt based on the total metal content.
- the nickel content the metal salt solution is preferably 0 to 50% by weight, in particular preferably up to 16% by weight.
- Copper and / or tin can be used in amounts of up to 30% by weight, preferably up to 10 wt .-%, based on the total metal content, are used.
- Particularly preferred embodiment of the method according to the invention follows the addition of the metal salt solution to the carboxylic acid suspension gradually in the Way that the content of dissolved carboxylic acid in the mother liquor during the Supply of the metal salt solution a value of 50% of the solubility of carboxylic acid not less than in water.
- the addition of the is particularly preferred Metal salt solution so gradually that until the suspended carboxylic acid dissolves the concentration of dissolved carboxylic acid does not fall below 80% of the solubility in Water falls below.
- the rate of addition of the metal salt solution to the Carboxylic acid suspension thus takes place in such a way that the withdrawal of carboxylic acid from the mother liquor including concentration reduction by dilution by the water supplied with the metal salt solution by the dissolution of not dissolved, suspended carboxylic acid is largely compensated.
- the solubility of the oxalic acid which is preferably used is in water approx. 1 mol per liter of water (room temperature), corresponding to 126 g oxalic acid (2nd Molecules of crystal water).
- the oxalic acid as an aqueous suspension the 2.3 to 4.5 moles of oxalic acid per liter of water contains.
- This suspension contains approximately 1.3 to 3.5 moles of undissolved Oxalic acid per liter of water.
- the content of oxalic acid in the mother liquor is said to be 20 to 55 g / l of water be.
- the metal salt solution is added in this way gradually that the oxalic acid concentration in the mother liquor during the addition not less than 75 g, particularly preferably not less than 100 g per liter of mother liquor decreases.
- a sufficiently high level of supersaturation is constantly achieved, which leads to nucleation, i.e. is sufficient to generate further precipitation particles.
- This will on the one hand high nucleation rate, which leads to correspondingly small particle sizes and, on the other hand, due to the small amount present in the mother liquor Metal ion concentration an agglomeration of the particles by dissolving largely prevented.
- the high carboxylic acid concentration preferred according to the invention during the precipitation also causes the precipitate to increase in relative levels
- Metals have the same composition as the metal salt solution, i.e. the existence homogeneous precipitation product with regard to its composition and thus alloy metal powder arises.
- Metal and alloy powders can be obtained by the process according to the invention be at least one of the elements iron, copper, tin, nickel or Contain cobalt and optionally by one or more of the elements Al, Cr, Mn, Mo, W can be doped in a minor amount, and the middle one Grain size according to ASTM
- B330 (FSSS) of 0.5 to 5 microns, preferably below 3 microns.
- the Alloy powders are characterized in that they are not produced by grinding Have fracture areas. You are with this immediately after the reduction Grain size available.
- Preferred metal or alloy particles have a very low carbon content of less than 0.04% by weight, preferably less than 0.01% by weight. This is due to that carried out between precipitation and reduction Temperature treatment in an oxygen-containing atmosphere attributable to the existing organic carbon is removed after the precipitation.
- preferred Metal or alloy powders also have an oxygen content of below 1% by weight, preferably less than 0.5% by weight.
- the preferred composition the alloy powder corresponds to the preferred relative metal contents of the metal salt solutions used, as indicated above.
- the available according to the invention Metal and alloy powders are extremely suitable as Binder metal for hard metals or diamond tools. They are also used for powder metallurgy Suitable for the production of components.
- example 1 2 3 4 Amount of water oxalic acid suspension (1) 15.6 ) 7.8 5.9 3.9 Particle size of the mixed oxalate ( ⁇ m, FSSS) 25.7 21.0 11.5 7.6 Alloy metal powders: particle size ( ⁇ m, FSSS) 2.1 ) 1.73 0.72 0.7 physical density (g / cm 3 ) 6.49 7.51 7.53 7.53 bulk density (g / cm 3 ) 0.44 0.38 0.26 0.24 oxygen content (Wt .-%) 0.96 0.81 0.69 0.70
- Sintered body Density (g / cm 3 ) 14.36 14.38 14.43 14.41 Vickers hardness HV 30 (kg / mm 2 ) 1785 1797 1814 1812 Porosity ASTM B 276 A04B02C00 A04B00C00 ⁇ A02B00C00 ⁇ A02B00C00 ⁇ A02B00C00
- a hard metal test was carried out on this metal powder under identical conditions as in Examples 1 to 4.
- the oxalate precipitation was carried out as in Example 5, but a Chloride solution with 42.7 g / l Co and 56.3 g / l Fe used.
- the calcination in the muffle furnace was carried out at 250 ° C.
- the three-step reduction below Hydrogen occurred at 520/550/570 ° C.
- Example 2 Analogously to Example 1, an iron-cobalt-copper oxalate was precipitated, washed and dried, a metal chloride solution containing about 45 g / l Fe, 45 g / l Co and 10 g / l Cu was used.
- the metal powders had the properties shown in Table 3.
- Example 7 A Example 7 B Sintering temperature ° C HRB SD % TD HRB SD % TD 580 105.8 7.55 88.95 110.9 7.92 93.83 620 111.1 8.05 94.84 111.3 8.22 97.38 660 111.2 8.19 96.49 110.6 8.22 97.38 700 110.6 8.19 96.49 109.8 8.22 97.38 740 109.6 8.20 96.6 107.5 8.22 97.38 780 109.6 8.19 96.49 108.6 8.24 97.62 820 108.6 8.18 96.37 104.4 8.24 97.62 860 106.6 8.20 96,60 106.2 8.23 97.5
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Manufacture And Refinement Of Metals (AREA)
Claims (4)
- Procédé pour la préparation de poudres de métaux et d'alliages contenant au moins un des métaux fer, cuivre, étain, cobalt ou nickel par mélange de solutions aqueuses de sels métalliques avec une solution aqueuse d'acide carboxylique, séparation du produit de précipitation et des liqueurs mères et réduction du produit de précipitation en métal, caractérisé en ce que la solution aqueuse d'acide carboxylique contient de l'acide carboxylique solide en quantité telle qu'après la précipitation, les liqueurs mères soient encore saturées à au moins 10 %, par rapport à la solution aqueuse sans les sels métalliques.
- Procédé selon la revendication 1, caractérisé en ce que, avant réduction en poudre d'alliage métallique, le produit de précipitation est soumis à décomposition thermique en atmosphère contenant de l'oxygène à des températures de 200 à 1 000°C.
- Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que la solution de sels métalliques est coulée dans la suspension aqueuse d'acide carboxylique.
- Procédé selon l'une des revendications 1 à 3, caractérisé en ce que la solution aqueuse de sels métalliques et l'acide carboxylique sont envoyés en continu dans un réacteur de précipitation d'où l'on évacue en continu les liqueurs mères contenant le produit de précipitation.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19822663A DE19822663A1 (de) | 1998-05-20 | 1998-05-20 | Sinteraktive Metall- und Legierungspulver für pulvermetallurgische Anwendungen und Verfahren zu deren Herstellung und deren Verwendung |
DE19822663 | 1998-05-20 | ||
PCT/EP1999/003170 WO1999059755A1 (fr) | 1998-05-20 | 1999-05-08 | Poudres de metal et d'alliage pour le frittage, a utiliser dans la metallurgie des poudres, leur procede de production et leur utilisation |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1079950A1 EP1079950A1 (fr) | 2001-03-07 |
EP1079950B1 true EP1079950B1 (fr) | 2003-08-13 |
Family
ID=7868428
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99923562A Expired - Lifetime EP1079950B1 (fr) | 1998-05-20 | 1999-05-08 | Poudres de metal et d'alliage pour le frittage, a utiliser dans la metallurgie des poudres, leur procede de production et leur utilisation |
Country Status (10)
Country | Link |
---|---|
US (1) | US6554885B1 (fr) |
EP (1) | EP1079950B1 (fr) |
JP (2) | JP4257690B2 (fr) |
KR (1) | KR100543834B1 (fr) |
CN (1) | CN1254339C (fr) |
AT (1) | ATE246976T1 (fr) |
AU (1) | AU4039399A (fr) |
CA (1) | CA2332889C (fr) |
DE (2) | DE19822663A1 (fr) |
WO (1) | WO1999059755A1 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102008052559A1 (de) | 2008-10-21 | 2010-06-02 | H.C. Starck Gmbh | Metallpulver |
EP2436793A1 (fr) | 2008-10-20 | 2012-04-04 | H.C. Starck GmbH | Poudre métallique |
US8523976B2 (en) | 2006-09-22 | 2013-09-03 | H.C. Starck Gmbh | Metal powder |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
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SE521488C2 (sv) | 2000-12-22 | 2003-11-04 | Seco Tools Ab | Belagt skär med järn-nickel-baserad bindefas |
BR0308703B1 (pt) * | 2002-03-29 | 2011-06-28 | pó pré-ligado. | |
US7799141B2 (en) * | 2003-06-27 | 2010-09-21 | Lam Research Corporation | Method and system for using a two-phases substrate cleaning compound |
CA2567800C (fr) * | 2004-05-28 | 2013-10-15 | Smith & Nephew, Inc. | Tige intramedullaire cannelee |
CN1868637B (zh) * | 2005-05-25 | 2010-04-21 | 成都平和同心金属粉末有限公司 | 铜合金包覆粉及制取方法 |
CN100509219C (zh) * | 2005-10-10 | 2009-07-08 | 中国科学院金属研究所 | 一种铁基扩散合金粉末的制备方法 |
FR2892957B1 (fr) * | 2005-11-09 | 2009-06-05 | Eurotungstene Poudres Soc Par | Poudre polymetallique et piece frittee fabriquee a partir de cette poudre |
CN100393454C (zh) * | 2005-11-25 | 2008-06-11 | 河南卡斯通科技有限公司 | 用于制备金刚石工具专用预合金粉的共沉淀法 |
CN101096053B (zh) * | 2006-06-29 | 2010-05-26 | 王世荣 | 一种钴铁超细合金粉的制备方法 |
DE102006045481B3 (de) * | 2006-09-22 | 2008-03-06 | H.C. Starck Gmbh | Metallpulver |
DE102006057004A1 (de) * | 2006-12-02 | 2008-06-05 | H.C. Starck Gmbh | Metallpulver |
DE102007004937B4 (de) * | 2007-01-26 | 2008-10-23 | H.C. Starck Gmbh | Metallformulierungen |
DE102007047312A1 (de) * | 2007-10-02 | 2009-04-09 | H.C. Starck Gmbh | Werkzeug |
DE602009000603D1 (de) * | 2008-05-21 | 2011-03-03 | Sandvik Intellectual Property | Verfahren zur Herstellung eines Verbunddiamantkörpers |
CN101428348B (zh) * | 2008-07-29 | 2010-09-08 | 张建玲 | 一种水热处理制备球形超细金属粉末的工艺方法 |
JP5546120B2 (ja) * | 2008-11-26 | 2014-07-09 | 京セラ株式会社 | サーメット製スローアウェイチップ |
US8216340B2 (en) * | 2009-03-03 | 2012-07-10 | E. I. Du Pont De Nemours And Company | Method for producing dispersed, crystalline, stable to oxidation copper particles |
JP5530270B2 (ja) * | 2010-06-29 | 2014-06-25 | Jx日鉱日石金属株式会社 | コバルト粉末及びその製造方法 |
EP2527480B1 (fr) | 2011-05-27 | 2017-05-03 | H.C. Starck GmbH | Liant NiFe ayant une application universelle |
CN102218709B (zh) * | 2011-06-03 | 2013-01-09 | 福建万龙金刚石工具有限公司 | 防脱落的金刚石布拉及其制作工艺 |
CN102419076B (zh) * | 2011-11-29 | 2013-07-17 | 济南沃德汽车零部件有限公司 | 气门烘干机 |
US20130178360A1 (en) * | 2012-01-06 | 2013-07-11 | California Institute Of Technology | Nickel-based electrocatalytic photoelectrodes |
JP5991645B2 (ja) * | 2012-12-28 | 2016-09-14 | 住友電気工業株式会社 | 金属粉末の製造方法 |
EP3142816A4 (fr) * | 2014-05-13 | 2017-12-27 | University Of Utah Research Foundation | Production de poudres métalliques sensiblement sphériques |
CN104874807A (zh) * | 2015-06-17 | 2015-09-02 | 北京科技大学 | 一种具有体心立方结构纳米铁钴固溶体合金粉末的制备方法 |
PL232405B1 (pl) | 2015-07-27 | 2019-06-28 | Akademia Gorniczo Hutnicza Im Stanislawa Staszica W Krakowie | Proszek stopowy na bazie żelaza, sposób jego wytwarzania i zastosowanie |
CN106180744A (zh) * | 2016-08-25 | 2016-12-07 | 董晓 | 一种金刚石制品用预合金粉末的制备方法 |
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GB419953A (en) | 1933-05-22 | 1934-11-22 | Telegraph Constr & Maintenance | Manufacture of nickel iron alloys |
GB610514A (en) * | 1943-03-01 | 1948-10-18 | Electro Chimie Metal | Improvements in or relating to the manufacture of iron powder and products produced therefrom |
US3923496A (en) * | 1945-04-26 | 1975-12-02 | Us Energy | Nickel powder and a process for producing it |
US3855016A (en) * | 1971-03-24 | 1974-12-17 | Graham Magnetics Inc | Acicular cobalt powders having high squarenesss ratios |
FR2587989B1 (fr) * | 1985-09-30 | 1987-11-13 | Centre Nat Rech Scient | Compositions particulaires d'oxalates de metaux ferromagnetiques, sous forme de particules aciculaires submicroniques, leur preparation et leur application |
DE3802811A1 (de) * | 1988-01-30 | 1989-08-10 | Starck Hermann C Fa | Agglomerierte metall-verbund-pulver, verfahren zu ihrer herstellung sowie deren verwendung |
WO1992018656A1 (fr) * | 1991-04-10 | 1992-10-29 | Sandvik Ab | Procede de fabrication d'articles en carbure cemente |
FR2723015B1 (fr) | 1994-07-29 | 1996-09-13 | Commissariat Energie Atomique | Procede d'obtention de poudres de fer ou a base d e fer par precipitation en phase liquide organique |
DE19540076C1 (de) * | 1995-10-27 | 1997-05-22 | Starck H C Gmbh Co Kg | Ultrafeines Kobaltmetallpulver, Verfahren zu seiner Herstellung sowie Verwendung des Kobaltmetallpulvers und des Kobaltcarbonates |
BE1009811A3 (fr) * | 1995-12-08 | 1997-08-05 | Union Miniere Sa | Poudre prealliee et son utilisation dans la fabrication d'outils diamantes. |
WO1998049361A1 (fr) | 1997-04-29 | 1998-11-05 | N.V. Union Miniere S.A. | Poudre pre-alliee a base de cuivre, et utilisation de cette poudre dans la fabrication d'outils en diamant |
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1998
- 1998-05-20 DE DE19822663A patent/DE19822663A1/de not_active Ceased
-
1999
- 1999-05-08 KR KR1020007012982A patent/KR100543834B1/ko not_active IP Right Cessation
- 1999-05-08 US US09/700,533 patent/US6554885B1/en not_active Expired - Fee Related
- 1999-05-08 WO PCT/EP1999/003170 patent/WO1999059755A1/fr active IP Right Grant
- 1999-05-08 AT AT99923562T patent/ATE246976T1/de active
- 1999-05-08 CA CA2332889A patent/CA2332889C/fr not_active Expired - Fee Related
- 1999-05-08 DE DE59906598T patent/DE59906598D1/de not_active Expired - Lifetime
- 1999-05-08 CN CNB998062944A patent/CN1254339C/zh not_active Expired - Fee Related
- 1999-05-08 JP JP2000549408A patent/JP4257690B2/ja not_active Expired - Fee Related
- 1999-05-08 EP EP99923562A patent/EP1079950B1/fr not_active Expired - Lifetime
- 1999-05-08 AU AU40393/99A patent/AU4039399A/en not_active Abandoned
-
2008
- 2008-07-30 JP JP2008196006A patent/JP2009001908A/ja active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8523976B2 (en) | 2006-09-22 | 2013-09-03 | H.C. Starck Gmbh | Metal powder |
EP2436793A1 (fr) | 2008-10-20 | 2012-04-04 | H.C. Starck GmbH | Poudre métallique |
DE102008052559A1 (de) | 2008-10-21 | 2010-06-02 | H.C. Starck Gmbh | Metallpulver |
Also Published As
Publication number | Publication date |
---|---|
AU4039399A (en) | 1999-12-06 |
DE59906598D1 (de) | 2003-09-18 |
CN1254339C (zh) | 2006-05-03 |
CA2332889C (fr) | 2010-04-06 |
CN1301205A (zh) | 2001-06-27 |
KR20010052366A (ko) | 2001-06-25 |
ATE246976T1 (de) | 2003-08-15 |
DE19822663A1 (de) | 1999-12-02 |
KR100543834B1 (ko) | 2006-01-23 |
US6554885B1 (en) | 2003-04-29 |
CA2332889A1 (fr) | 1999-11-25 |
EP1079950A1 (fr) | 2001-03-07 |
JP4257690B2 (ja) | 2009-04-22 |
WO1999059755A1 (fr) | 1999-11-25 |
JP2009001908A (ja) | 2009-01-08 |
JP2002515543A (ja) | 2002-05-28 |
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